JPH04226967A - Method and apparatus for continuously reacting cyanuric fluoride with amine - Google Patents

Abstract

PURPOSE: To obtain a cyanur fluoride-amine condensate at a high yield with high purity.

CONSTITUTION: This invention relates to the continuous reaction method for introducing the cyanur fluoride and an aq. amine soln. (more particularly an aq. soln. of aminonaphthol sulfonic acid) at different rates into a reactor 1 to cause vigorous mixing, substantially completing the reaction without back mixing in this reactor and taking out the reactants, and the reaction apparatus which is suitable for this reaction method and consists of the reactor 1, nozzles 2 and 4 and reactant supply pipes 3 and 5 respectively connected thereto. The nozzle 2 opens in an axial direction in order to introduce the one reactant into the reactor 1 and the plural nozzles 4 open to concentrically enclose the same, through which the another reactant is supplied to the reactor 1.

COPYRIGHT: (C)1992,JPO

Description

[Detailed description of the invention]

The present invention relates to a process for the continuous reaction of cyanuric fluoride and an amine by introducing an aqueous solution of the cyanuric fluoride and the amine into the reactor, and a reactor for carrying out this process.

DE-C2-2746109 describes a process for the continuous reaction of cyanuric fluoride with aminobenzenesulfonic acid or aminonaphthalenesulfonic acid, in which the reactor used is combined with complete back-mixing. It is an "ideal tank" that allows reactants to flow in continuously. However, this known method can only be applied to a limited extent for the reaction of cyanuric fluoride with aminonaphtholsulfonic acid, since in this case considerable amounts of by-products are formed. do not have.

In addition, EP-A2-0172790 describes a process for the continuous reaction of cyanuric fluoride with aminobenzenesulfonic acid or aminonaphthalenesulfonic acid, in which An aqueous solution of cyanuric and amine is introduced simultaneously and continuously into a first reactor and mixed vigorously therein, and the resulting reaction mixture is subsequently introduced into a second reactor, in which minimal Only back-mixing of 200 ml occurs, but complete radial mixing occurs and completes the reaction therein.

However, this method has several drawbacks, namely the need for a second reactor and the DE
Although this is reduced compared to the process described in C2-2746109, it still has the disadvantage that disadvantageously high amounts of by-products are produced.

The problem posed by the present invention is that amino condensates,
That is, an improved method of combining cyanuric fluoride with an amine containing a sulfonic group and a chromophore, more particularly aminonaphthol sulfonic acid, into a mixture obtainable by the reaction of 1 mole of cyanuric fluoride with 1 mole of amine. The objective was to provide a method and a reactor for continuous reactions giving yields and/or purity.

According to the invention, a solution to this problem is to introduce the reactants simultaneously and successively into the reactor at different rates, and to cause intense mixing by the difference in flow rates, and to allow this reactor to flow without back-mixing. It is characterized by completing the reaction inside.

Surprisingly, with this process it is possible to achieve conversions of at least 95% in a single reaction step.

In one particular embodiment of the new process, cyanuric fluoride is present in the reactor at a concentration of at least 10,000
0, preferably at least 15,000, while the aqueous amine solution enters the reactor at a Reynolds number of at least 2,500, preferably at least 5,000, and the cyanuric fluoride stream and the aqueous amine stream The difference between the flow velocities is at least 20 m/s, preferably at least 40 m/s.

These measures ensure particularly intensive mixing over a very short period of time without backflow.

The ratio of the cross section of the reactor to the inlet cross section of the cyanuric fluoride stream is preferably from 225 to 4,000, more preferably from 700 to 12,000. Application of this cross-sectional ratio to the mass flow optimizes mixing of reactants without backflow.

The residence time in the reactor is preferably at most 5 seconds, more particularly 0.2 to 2 seconds.

This residence time is sufficient for almost complete reaction.

In another embodiment of the novel process, the reaction is carried out at a temperature of 0 to 50°C, preferably 0 to 20°C.

The new method uses 2,4,6-trifluoro-S
- Particularly suitable for the reaction of triazines with sulfo-containing anilines and naphthylamines or with sulfo-containing aminophenols and for the reaction of 2,4,6-trifluoro-S-triazines with chromophore-containing amines ing.

A tubular reactor is used, into which the cyanuric fluoride is introduced in an axial jet, while the amine solution is introduced as a concentric jet at different speeds ensuring intensive mixing, and this The reaction is brought to substantial completion in the reactor.

When this procedure is applied, intense mass transfer occurs at the interface between both jets.

Surprisingly, the reaction product of 1 mol of aminonaphtholsulfonic acid and 1 mol of cyanuric fluoride can also be obtained in high yield and purity by application of this method. In many cases, the process of the invention is superior to known processes for the reaction of aminobenzene or aminonaphthalene sulfonic acid or chromophore-containing amines with cyanuric fluoride.

However, the process according to the invention can also be carried out using ammonia or aliphatic amines such as ethanolamine, morpholine or taurine. However, preference is given to using aromatic amines containing sulfo groups and chromophore-containing amines, the negative charge of the sulfo group being neutralized by quaternary, especially aliphatic, ammonium ions.

Examples of suitable aromatic amines containing sulfo groups are 1-aminobenzene-2-sulfonic acid, 1-aminobenzene-3-sulfonic acid, 1-aminobenzene-4-
Sulfonic acid, 1-amino-4-methylbenzene-3-sulfonic acid, 1-amino-4-methoxybenzene-3-sulfonic acid, 1-amino-2-methylbenzene-4-sulfonic acid, 1-amino-3 -Methylbenzene-4-sulfonic acid, 1-aminobenzene-3,5-disulfonic acid, 2
-Amino-5-sulfobenzoic acid, 1-aminonaphthalene-4-sulfonic acid, 1-aminonaphthalene-5-sulfonic acid, 1-aminonaphthalene-6-sulfonic acid, 2-aminonaphthalene-5-sulfonic acid, 2 -aminonaphthalene-7-sulfonic acid, 2-aminonaphthalene-4,8-
Disulfonic acid, 2-aminonaphthalene-5,7-disulfonic acid, 1,4-diaminobenzene-2,5-disulfonic acid, 1,3-diaminobenzene-4-sulfonic acid, 1
, 4-diaminobenzene-2-sulfonic acid, 1,3-diaminobenzene-4,6-disulfonic acid, 1-amino-
5-hydroxynaphthalene-7-sulfonic acid, 1-amino-8-hydroxynaphthalene-4-sulfonic acid, 1-
amino-8-hydroxynaphthalene-3-sulfonic acid,
1-amino-8-hydroxynaphthalene-5-sulfonic acid, 2-amino-5-hydroxynaphthalene-7-sulfonic acid, 2-amino-6-hydroxynaphthalene-8-
Sulfonic acid, 2-amino-8-hydroxynaphthalene-
6-sulfonic acid, 2-methylamino-5-hydroxynaphthalene-7-sulfonic acid, 2-ethylamino-5-hydroxynaphthalene-7-sulfonic acid, 2-methylamino-8-hydroxynaphthalene-6-sulfonic acid, 2-
Ethylamino-8-hydroxynaphthalene-6-sulfonic acid, 1-amino-6-hydroxynaphthalene-3,8
-disulfonic acid, 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid, 1-amino-8-hydroxynaphthalene-2,4-disulfonic acid, 1-amino-8-hydroxynaphthalene-2,4-disulfonic acid
-Hydroxynaphthalene-4,6-disulfonic acid, 1-
Amino-8-hydroxynaphthalene-3,5-disulfonic acid, 2-amino-5-hydroxynaphthalene-7,1
-disulfonic acid and 2-amino-8-hydroxynaphthalene-3,6-disulfonic acid.

The method of the present invention comprises cyanuric fluoride and 2-amino-5-hydroxynaphthalene-7-sulfonic acid, 2-
amino-8-hydroxynaphthalene-6-sulfonic acid,
Especially for the reaction of 1-amino-8-hydroxynaphthalene-4,6-disulfonic acid or, inter alia, 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid or 1-aminobenzene-3-sulfonic acid. Are suitable.

The amine containing a sulfo group or a chromophore is used in the form of an aqueous solution. Cyanuric fluoride may be used in relatively large excess. Cyanuric fluoride and amine 0.8:
It is best to use a molar ratio of 1 to 1.5:1, preferably 1:1 to 1.2:1, more preferably 1:1 to 1.08:1.

During the reaction, it is preferred to add a buffer substance to the amine solution to keep the pH value in the range 1 to 8, preferably in the range 3 to 5, depending on the substance. Suitable buffer substances are, for example, alkali metal fluorides, borates and phosphates, more particularly NaF. These buffer substances are generally used in amounts of 0.00% per mole of amine.
It is used in amounts of 2 to 2 mol, preferably 0.4 to 1.2 mol.

The reaction products of 1 mole of amine and 1 mole of cyanuric fluoride thus formed may be isolated, but without isolation, by reaction with other amines or dyes containing amino groups, Alternatively, they can be processed to give reactive dyes by reaction with aromatic amines and subsequent coupling with diazonium compounds. This subsequent treatment can be carried out batchwise or continuously in a known manner.

In many cases, the process of the invention gives condensates of cyanuric fluoride and aromatic amines containing sulfo groups or chromophores in significantly higher purity than conventional processes. This has an advantageous effect on the quality of the reactive dyes produced from the condensate, since the condensate is generally processed further without purification.

The new process can be carried out in a variety of reactors as long as the reactants can be mixed vigorously without backmixing and the reaction mixture can be passed through continuously.

One reactor which has been found to be particularly suitable for carrying out the new process has one nozzle opening axially into the tube and concentrically thereto for introducing the reactants. It is a tubular reactor with one or more open nozzles.

In one preferred embodiment, the concentrically open nozzle outlet direction is inclined by 45 to 90° with respect to the axial nozzle outlet direction. This provides particularly intense mass transfer between both reactant streams.

The tubes continue in the direction of flow and are used to dissipate the reaction products after the reaction zone, but the reaction zone, which begins immediately after the opening of the nozzle, extends over only a small distance. . Two-component nozzles, ie a central nozzle and an annular gap surrounding it, are particularly suitable for introducing the reactants, with the cyanuric fluoride being introduced centrally and the aqueous amine solution being introduced concentrically thereto.

A preferred new reactor will be described in detail below with reference to the accompanying schematic drawings.

The supply pipe 3 for 2,4,6-trifluoro-S-triazine (cyanuric fluoride) has a length of 0.03 m.
A nozzle 2 with a cross section F1 of m2 opens axially into a reaction tube 1 with a circular cross section FR of 80 mm2. 64 connected to the supply pipe 5 for the amine aqueous solution
An annular nozzle 4 with a cross section F2 of mm2 concentrically surrounds the supply pipe 3. The length L of the reaction zone 5 is the product of the residence time of cyanuric fluoride and the amine solution of 5 seconds, preferably 2 seconds, and the total flow rate of both. The following tube section 6 is used for transporting the reaction products.

Instead of an annular nozzle 4, a plurality of individual nozzles or nozzle openings may also be distributed around the circumference.

[0032]

Example 1: 5.4 liters/hour of cyanuric fluoride and 0.26 mol/liter of 1-amino-8-hydroxynaphthalene-3,6 with a temperature of about 20° C. and a Reynolds number of 16,000. -disulfonic acid, 0.1 mol/
liter of NaF and 0.26 ml/liter of NaO
225 l/h of an aqueous solution containing H and having a temperature of 0° C. and a Reynolds number of 8000, simultaneously and continuously through separate feed pipes 3 and 5 or nozzle openings 2 and 4 of the type shown in FIG. into the reactor. The ratio between the flow cross section FR of reactor 1 and the flow cross section F1 of nozzle 2 is 2,660.

Cyanuric fluoride is ejected into the aqueous amine solution at a flow rate difference of 49 m/sec. The residence time in the reaction zone is approximately 0.7 seconds, ie, the reaction is substantially complete within this time.

At a temperature of 9° C. the reaction zone L (L=570 mm
) contains a compound of the following formula in a yield of 93±2%, based on the 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid used:

003
5]

[Chemical formula 1]

For comparison, European Patent No. A-172
When using the method according to No. 790 (page 6, top), only a yield of 85% is obtained in this reaction step.

The reaction mixture obtained is introduced into a stirred tank and converted into a red reactive dye by the following procedure.

For each mole of the above condensate, 1 mole of p-chloroaniline, 500 ml of water and 100 ml of 32%
Add hydrochloric acid to the reaction mixture and dilute to 1 with 20% NaOH.
Establish a pH value of 0.6 over a period of 0-20 minutes.

The solution obtained is added to a diazonium salt suspension at 0-5° C. obtained by diazotization of 1 mol of 2-naphthylamine-1,5-disulfonic acid by standard methods. A pH value of 7.5 is established at a maximum of 10° C. by adding 30% sodium hydroxide with vigorous stirring, followed by stirring for 1 hour at pH 7.5/10° C.

A dye corresponding to the following formula is obtained which is capable of dyeing cellulose materials in red tones:

[0041]

[Case 2]

[0042]

Example 2 5.4 l/h of cyanuric fluoride and 0.26 mol/l of 1-amino-8-hydroxynaphthalene-3,6- with a temperature of about 20°C and a Reynolds number of 16,000 225 liters/hour of an aqueous solution containing disulfonic acid, 0.1 mol/liter NaF and 0.26 mol/liter morpholine and having a temperature of 0° C. and a Reynolds number of 8,000 were fed into a separate feed tube 3. and 5 into a reactor of the type shown in FIG. 1 through nozzle openings 2 and 4. The ratio between the flow cross section FR of reactor 1 and the flow cross section F1 of nozzle 2 is 2,660.

Cyanuric fluoride is jetted into the aqueous solution at a flow velocity difference of 49 m/sec.

The residence time in reactor 1 corresponding to a length L of 570 mm is 0.7 seconds.

The reaction mixture leaving the reactor at a temperature of 9° C. is in the form of the morpholine salt of the formula

[0046]

[Chemical formula 3]

Contains the following compound. Yield is 93±2%.

By adjusting the pH value to 7 with LiOH, the coupling component:

[0049]

[C4]

was obtained and further treated by diazotization as in Example 1 to obtain the following formula:

[0051]

[C5]

A dye corresponding to ##STR11## is obtained. This dye dyes cellulose in a blue-red shade with very high wet fastness.

The main features and aspects of the present invention are as follows.

1. The reactants are introduced simultaneously and continuously at different rates into the reactor (1), with the difference in flow rates producing intense mixing and without back-mixing.
1) characterized in that the reaction is substantially completed in the
A continuous reaction method for cyanuric fluoride and an amine, which comprises continuously introducing a cyanuric fluoride and an aqueous amine solution into a reactor (1) and then removing the reaction product.

2. At least 10,000 cyanuric chloride
The aqueous amine solution is simultaneously introduced into the reactor (1) at a Reynolds number of 0 and the aqueous amine solution is introduced at a Reynolds number of at least 2,500 such that the difference in flow velocity between the cyanuric fluoride stream and the amine solution stream is at least 20 m/s, preferably 40 m/s. 2. The method according to item 1 above, characterized in that: /second.

3. The method according to item 2 above, characterized in that the ratio of the reactor cross section FR to the inlet cross section F1 of the cyanuric fluoride flow is maintained at 225 to 40,000, preferably 700 to 12,000.

4. The method according to item 1, 2 or 3 above, characterized in that the residence time in the reactor (1) is at most 5 seconds.

5. 5. The method described in items 1 to 4 above, wherein the reaction is carried out at a temperature of 0 to 50°C.

6. The method according to items 1 to 5 above, characterized in that 2,4,6-trifluoro-S-triazine is reacted with sulfo group-containing aniline and naphthylamine or sulfo group-containing aminonaphthol. Method.

7. The method according to any of the above items 1 to 5, characterized in that 2,4,6-trifluoro-S-triazine is reacted with a chromophore-containing amine.

8. Cyanuric chloride and amine, characterized in that a nozzle (2) opens axially into the tube (1) for the introduction of the reactants and one or more nozzles (4) open concentrically thereto. reactor for the continuous reaction of

9. The exit direction of the concentrically open nozzle (4) is 45 mm with respect to the exit direction of the axial nozzle (2).
9. The device according to claim 8, wherein the device is tilted by ~90°.

10. 10. The apparatus according to item 8 or 9, characterized in that the ratio of the reactor cross section FR to the inlet cross section F1 of the cyanuric fluoride flow is 400 to 12,000.

[Brief explanation of the drawing]

FIG. 1 shows a cross section of the reactor.

FIG. 2 shows part A of the nozzle, half in cross section, on an enlarged scale;

Claims (2)

[Claims] 1. The reactants are introduced simultaneously and successively at different rates into the reactor (1), with the difference in flow rates producing intense mixing, without back-mixing.
1) characterized in that the reaction is substantially completed in the
A continuous reaction method for cyanuric fluoride and an amine, which comprises continuously introducing a cyanuric fluoride and an aqueous amine solution into a reactor (1) and then removing the reaction product. 2. characterized in that a nozzle (2) is axially open in the tube (1) for the introduction of the reactants and one or more nozzles (4) are open concentrically thereto; Reactor for the continuous reaction of cyanuric chloride and amines.